Methods of cementing using a fluid loss control additive

ABSTRACT

A method of cementing, comprising displacing a cement composition into a workspace, wherein the cement composition comprises cement, water, and a fluid loss control additive comprising a polymer and a sugar connected by a pH-sensitive crosslink, and allowing the cement composition to set. A method for reducing fluid loss from a cement composition, comprising providing a cement and a fluid loss control additive, wherein the fluid loss control additive comprises a polymer and a sugar connected by a pH-sensitive crosslink, and mixing the cement, fluid loss control additive, and water to form the cement composition.

CROSS REFERENCE TO RELATED APPLICATIONS

Related co-pending application concurrently filed is U.S. patentapplication Ser. No. 11063,006 entitled “Fluid Loss Control Additive andCement Compositions Comprising Same,” which is incorporated by referenceherein in its entirety.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to the field of cement compositions and morespecifically to the field of using cement compositions comprising fluidloss control additives to service a wellbore.

2. Background of the Invention

A natural resource such as oil or gas residing in a subterraneanformation can be recovered by drilling a well into the formation. Thesubterranean formation is usually isolated from other formations using atechnique known as well cementing. In particular, a wellbore istypically drilled down to the subterranean formation while circulating adrilling fluid through the wellbore. After the drilling is terminated, asting of pipe, e.g., casing, is run in the wellbore. Primary cementingis then usually performed whereby a cement slurry is pumped down throughthe string of pipe and into the annulus between the string of pipe andthe walls of the wellbore to allow the cement slurry to set into animpermeable cement column and thereby seal the annulus. Secondarycementing operations may also be performed after the primary cementingoperation. One example of a secondary cementing operation is squeezecementing whereby a cement slurry is forced under pressure to areas oflost integrity in the annulus to seal off those areas.

The cement compositions typically include a fluid loss control additiveto reduce the loss of fluid, e.g., water, from the cement compositionswhen in contact with permeable subterranean formations and zones. Fluidloss from the cement composition may cause problems such as prematuredehydration. Premature dehydration of the cement may lead to problemssuch as limits on the amount of cement composition that can be pumped; adecrease in the compressive strength of the cement composition; and anegative impact bond strength between the set cement composition and asubterranean zone, the walls of pipe and/or the walls of the wellbore.

Large, water-soluble polymers such as copolymers of acrylamide and2-acrylamido, 2-methyl propane sulfonic acid have typically been used assynthetic fluid loss control additives. However, such fluid loss controladditives may lead to problems such as being useful in a limited numberof operations. For instance, the copolymers may not be efficient athigher wellbore circulating temperatures. Moreover, the copolymers mayaffect the rheology of the cement composition as they may exhibit highviscosity and poor mixability, which may lead to the need of asufficiently large amount of fluid loss control additive to create acement composition having an acceptable fluid loss. Such a sufficientlylarge amount of fluid loss control additive may lead to viscosity andpumpability problems. In addition, some copolymers may not have a salttolerance suitable for applications involving cement compositionscomprising salts. Further drawbacks include that synthetic polymers maynot comply with environmental regulations in certain regions of theworld. For example, the use of polyamide polymers in the North Sea maybe problematic because of the high molecular weight and poorbiodegradability of such synthetic polymers.

Consequently, there is a need for a fluid loss control additive thatthat is suitable for use in a wider range of wellbore circulatingconditions. In addition, needs include a fluid loss control additivethat is more compliant with environmental regulations. Additional needsinclude a biodegradable fluid loss control additive. Further needsinclude a more efficient cement composition comprising a fluid losscontrol additive.

BRIEF SUMMARY OF SOME OF THE PREFERRED EMBODIMENTS

Disclosed herein is a method of cementing, comprising displacing acement composition into a workspace, wherein the cement compositioncomprises cement, water, and a fluid loss control additive comprising apolymer and a sugar connected by a pH-sensitive crosslink, and allowingthe cement composition to set.

Further disclosed herein is a method for reducing fluid loss from acement composition, comprising providing a cement and a fluid losscontrol additive, wherein the fluid loss control additive comprises apolymer and a sugar connected by a pH-sensitive crosslink, and mixingthe cement, fluid loss control additive, and water to form the cementcomposition.

The cement composition comprising a polymer such as polyvinyl alcoholand sugars such as sorbitol overcomes problems in the art such asinefficiency as a fluid loss control additive at higher wellborecirculating temperatures. For instance, at higher temperatures, thecement composition does not require sufficiently large amounts of thePVA and sorbitol. In addition, the PVA and sorbitol may be moreefficient with cement compositions comprising salts.

The foregoing has outlined rather broadly the features and technicaladvantages of the present invention in order that the detaileddescription of the invention that follows may be better understood.Additional features and advantages of the invention will be describedhereinafter that form the subject of the claims of the invention. Itshould be appreciated by those skilled in the art that the conceptionand the specific embodiments disclosed may be readily utilized as abasis for modifying or designing other structures for carrying out thesame purposes of the present invention. It should also be realized bythose skilled in the art that such equivalent constructions do notdepart from the spirit and scope of the invention as set forth in theappended claims.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

In an embodiment, a cement composition includes a cement, water, and afluid loss control additive comprising a complex of a crosslinkedpolymer and a sugar. The polymer and the sugar are connected by apH-sensitive crosslink and may provide a fluid loss control additivethat is biodegradable. In some embodiments, the fluid loss controladditive is an emulsion also including a hydrophobic carrier fluid. Inother embodiments, the fluid loss control additive comprises a polyvinylalcohol complex.

The cement compositions are suitable for subterranean applications suchas well completion and remedial operations. It is to be understood that“subterranean applications” encompass both areas below exposed earth andareas below earth covered by water such as ocean or fresh water. In someembodiments, the cement compositions include a sufficient amount ofwater to form a pumpable slurry. The cement compositions may comprise adensity of from about 4 lb/gallon to about 23 lb/gallon. In alternativeembodiments, the cement compositions may comprise a density of fromabout 12 lb/gallon to about 17 lb/gallon. In other alternativeembodiments, the cement compositions may be low-density cementcompositions with a density of from about 5 lb/gallon to about 12lb/gallon.

The cement composition comprises a cement such as hydraulic cement,which includes calcium, aluminum, silicon, oxygen, and/or sulfur andwhich sets and hardens by reaction with water. Examples of hydrauliccements include but are not limited to Portland cements (e.g., classesA, C, G, and H Portland cements), pozzolana cements, gypsum cements,phosphate cements, high alumina content cements, silica cements, highalkalinity cements, and combinations thereof.

A sufficient amount of water is added to the cement to form a pumpablecementitious slurry. The water may be fresh water or salt water, e.g.,an unsaturated aqueous salt solution or a saturated aqueous saltsolution such as brine or seawater, or a non-aqueous fluid. The watermay be present in the amount of from about 16 to about 180 percent byweight of cement, alternatively from about 28 to about 60 percent byweight of cement.

The cement compositions comprise a sufficient amount of the fluid losscontrol additive to provide a desired level of fluid loss control in acement composition. In an embodiment, the fluid loss control additivemay be present in the cement compositions in an amount from about 0.01to about 10.0 percent by weight of the cement. In another embodiment,the fluid loss control additive may be present in the cement compositionin an amount from about 0.2 to about 1.4 percent by weight of thecement. Fluid loss control additives comprising pH-sensitive crosslinkedpolymers are disclosed in U.S. Pat. No. 6,739,806, which is incorporatedherein by reference in its entirety. In an embodiment, the fluid losscontrol additive does not increase viscosity of the cement composition.

The fluid loss control additive comprises a complex of a polymer and asugar connected by a pH-sensitive crosslink (e.g., a borate ester ofpolyvinyl alcohol). In an embodiment, the fluid loss control additivecomprises a weight ratio of polymer to sugar of from about 1:3 to about10:1, alternatively from about 1:2 to about 5:1. The pH-sensitivecrosslink between the polymer and the sugar is achieved through the useof a polyvalent cation which may be referred to as a crosslinker. Anypolyvalent cation capable of connecting two or more polymer strandsthrough a pH-sensitive crosslink may be suitable for use with the fluidloss control additives. It is to be understood that one of ordinaryskill in the art with the benefit of this disclosure would be able torecognize the appropriate polyvalent cation for use in a particularapplication. In some embodiments, the polyvalent cation comprises aGroup IIIA element such as boron or aluminum or a Group IVB element suchas titanium or zirconium. In some embodiments, the boron may be providedby a borate ion. Examples of suitable sources of borate ions includewithout limitation borax, sodium borate, boric acid and combinationsthereof. An example of a suitable source of borate ion is reagent gradeboric acid, which is commercially available from Sigma Aldrich, Inc. Inan embodiment, the fluid loss control additive contains the polyvalentcation in the amount of from about 0.001 to about 5 percent by weight ofthe polymer, alternatively from about 0.05 to about 0.2 percent byweight of the polymer.

The pH-sensitive nature of the crosslink between the polymer and thesugar may improve the degradability of the fluid loss control additivesof the present invention. Without being limited by theory, thepH-sensitive nature of the crosslink may cause the crosslinked polymerand sugar to fall apart in a solution of water having a pH within aparticular range, depending on the polyvalent cation used to make thecrosslink. In some embodiments wherein the polyvalent cation comprisesboron, the crosslinked polymer and sugar may fall apart in a solution ofwater having a pH below about 9.2. It is to be understood that thetypical cement composition has a pH ranging from about 10 to about 13.Therefore, the fluid loss control additive may be substantially stablewhen placed in such a typical cement composition. However, inembodiments wherein such a pH-sensitive crosslink is placed into asource of free water (e.g., seawater), the crosslink between the polymerand the sugar may be broken, thus releasing into the seawater a lowermolecular weight polymer that may be more likely to biodegrade.

A sugar refers to a water-soluble crystalline carbohydrate. Examples ofsuitable sugars include without limitation monosaccharides,disaccharides, and trisaccharides. In some embodiments, the sugarprovides the base monomer for PVA. In one embodiment, the sugar is asugar alcohol. Sugar alcohols refer to polyols having more than threehydroxyl groups. Such sugar alcohols are represented by the followinggeneral formula:CH₂OH(CHOH)_(n)CH₂OH,where n may be from 2 to 5. Without limitation, examples of sugaralcohols include sorbitol, maltitol, isomalt, xylitol, lactitol,hydrogenated starch hydrolysates, and combinations thereof. In someembodiments, the sugar alcohol is sorbitol. Sorbitol is a white,sweetish crystalline alcohol that is found naturally in fruits andvegetables. It is represented by the chemical formula C₆H8(OH)₆, whichmay be represented by the following structure.

In some embodiments, the polymers may comprise polyalcohols; alphahydroxy acids; 1,2 amines; and combinations thereof. Examples ofsuitable polyalcohols include without limitation 1,2 alcohols and 1,3alcohols. Without limitation, an example of a suitable 1,2 alcohol ispolysaccharide (e.g., guar gum), and an example of a suitable 1,3alcohol is a polyvinyl alcohol. Examples of commercially availablepolyvinyl alcohols include ERKOL 40/140, which is available from CrossWorld Sale Corporation.

In some embodiments, the fluid loss control additive comprises anemulsion, which includes the polymer, the sugar, and a carrier fluid. Insome embodiments, the carrier fluid may be a hydrophobic carrier fluidsuch as a vegetable oil. Without limitation, examples of suitablevegetable oils include soybean oil, corn oil, grape seed, coconut oil,rape oil, and combinations thereof. The fluid loss control additive maycontain an amount of the carrier fluid suitable for forming theemulsion. In an embodiment, the fluid loss control additive may comprisefrom about 1 to about 90 wt. % carrier fluid, from about 50 to about 90wt. % carrier fluid, alternatively from about 60 to about 70 wt. %carrier fluid.

The fluid loss control additive may also contain a sufficient amount ofwater to form a pumpable emulsion. The water may be fresh water or saltwater, e.g., an unsaturated aqueous salt solution or a saturated aqueoussalt solution such as brine or seawater, or a non-aqueous fluid. Thefluid loss control additive may comprise from about 5 to about 25 wt. %water, alternatively from about 10 to about 20 wt. % water. In anembodiment, the cement composition may contain the emulsion in an amountfrom about 0.02 to about 5 percent by weight of the cement,alternatively from about 0.2 to about 3 percent by weight of the cement,and alternatively from about 0.5 to about 1.5 percent by weight of thecement.

In other embodiments, the emulsion may also contain an emulsifier suchas a surfactant. Without limitation, examples of suitable surfactantsinclude ethoxylated glyceryl fatty acid esters such as withoutlimitation PEG 20 glyceryl laurate, PEG 20 glyceryl oleate, PEG 20glyceryl oleoricinoleate, and PEG 20 glyceryl stearate; sorbitan estersand ethoxylated sorbitan esters such as without limitation sorbitanmonolaurate, sorbitan trioleate, PEG 20 sorbitan monolaurate, PEG 20sorbitan trioleate, and PEG 4 sorbitan monolaurate; and imidazole fattyacid condensates. Such suitable cement surfactants are available fromHalliburton Energy Services, Inc. as MOC-ONE and DOC-3. The emulsion mayinclude from about 0.1 to about 10.0 wt. % emulsifier, alternativelyfrom about 0.5 to about 10.0 wt. % emulsifier.

The fluid loss control additive can be prepared in a variety of ways. Inan embodiment, the fluid loss control additive is made by mixing thepolymer and the sugar in a solvent to form a mixture, adding apolyvalent cation to the mixture, and adjusting the pH as necessary tocrosslink the polymer and sugar until the resulting solution achieves adesired molecular weight. In an embodiment, the mixture of the solvent,polymer, and sugar may comprise from about 5 to about 50 wt. % ofpolymer and sugar combined. Adjusting the pH includes adding an aqueoussolution of a base to the solution to adjust the pH to a desired value.The polymer/sugar complex solution is then dried to isolate the complexas a powder. To form an emulsion containing the complex, the hydrophobiccarrier fluid is mixed with water and then emulsified with a surfactant.The powder complex is added to the emulsion while stirring andafterwards mixed.

In another embodiment, the fluid loss control additive is formed in asuspension of the polymer and the sugar in an inert solvent. A desiredamount of polyvalent cation and a base are added as aqueous solution toadjust the pH. After the complex formation of the fluid loss controladditive is complete, the solvent is removed by distillation to providethe complex in powder form, which is then dried (e.g., in a vacuumoven). To form an emulsion containing the dried complex, the hydrophobiccarrier fluid is mixed with water and then emulsified with a surfactant.The powder complex is added to the emulsion while stirring andafterwards mixed.

In still another embodiment, the fluid loss control additive complex isdirectly formed in the hydrophobic carrier fluid. The hydrophobiccarrier fluid is mixed with water then emulsified with a surfactant. Thepolymer and the sugar are added and crosslinked with a polyvalent cationand a base, which adjusts the pH. The emulsion is then mixed.

Examples of suitable solvents include without limitation water and2-propanol. Without limitation, an example of a suitable base includessodium hydroxide. In an embodiment, the pH can be adjusted until thesolution has a molecular weight from about 5,000 to about 500,000,alternatively from about 50,000 to about 250,000. It is to be understoodthat one of ordinary skill in the art with the benefit of thisdisclosure will be able to identify suitable methods of measuringmolecular weight of the solution and also will be able to recognize whena sufficient degree of crosslinking has been achieved. One such suitablemethod of detection is multi-angle light scattering HPLC. It is to beunderstood that any suitable method of mixing the solution with thecarrier fluid, water, and emulsifier may be used.

The fluid loss control additives may be added to the cement compositionsin a variety of ways. For instance, the dry cement, water and fluid losscontrol additive may be mixed in any order and given sufficient time tolet the fluid loss control additive hydrate. In some instances, the drymaterials may swell when contacted with water. In such instances, anappropriate waiting period for hydration may be about 10 minutes afterthe end of visible swelling. In other instances, the fluid loss controladditives may be added according to standard American PetroleumInstitute (API) procedures.

In some embodiments, the cement composition is a low-density cementcomposition such as a foamed cement composition or one that includesdensity reducing additives. For a foamed cement composition, anembodiment may include the foamed cement composition comprising foamingagents, foam stabilizing agents, and combinations thereof, which may beincluded in the cement composition to facilitate the foaming and/orenhance the stability of the cement composition. Such foaming and/orfoam stabilizing agents may be present in the cement composition in anamount sufficient to provide a stable, foamed cement composition. It isto be understood that one of ordinary skill in the art would be able toselect the proper foaming and/or foam stabilizing agents as well as theamounts of such agents according to the particular application.

In an embodiment, the foamed cement composition may include an expandingadditive. The expanding additive may be any component that enables a gasto become incorporated into the cement composition. Without limitation,examples of suitable expanding additives in particulate form includealuminum powder, gypsum blends, deadburned magnesium oxide, andcombinations thereof. Examples of expanding additives comprisingaluminum powder that are commercially available include “GAS-CHEK” and“SUPER CBL” from Halliburton Energy Services, Inc. An example of anexpanding additive comprising a blend containing gypsum is commerciallyavailable as “MICROBOND” from Halliburton Energy Services, Inc. Inaddition, examples of expanding additives comprising deadburnedmagnesium oxide are commercially available as “MICROBOND M” and“MICROBOND HT” from Halliburton Energy Services, Inc. Such expandingadditives are described in U.S. Pat. Nos. 4,304,298; 4,340,427;4,367,093; 4,450,010 and 4,565,578, which are incorporated herein byreference in their entirety. The cement composition may contain anamount of the expanding additive from about 2 to about 18 wt. %,alternatively from about 5 to about 10 wt. %.

The addition of an expanding additive to the cement composition may beaccomplished by any suitable method. In one embodiment, the cementcomposition is foamed by direct injection of an expanding additive intothe cement composition. For instance, where the cement composition isfoamed by the direct injection of gas into the cement composition, thegas utilized may be air, an inert gas such as nitrogen, and combinationsthereof. In other embodiments, the cement composition is foamed by gasgenerated from a reaction between the cement composition and anexpanding additive present in the cement composition in particulateform. For example, the cement composition may be foamed by hydrogen gasgenerated in situ as the product of a reaction between the high pHslurry and fine aluminum powder present in the cement.

In an embodiment, a low-density cement composition includes densityreducing additives. Without limitation, examples of density reducingadditives include hollow glass beads, microspheres, and combinationsthereof. The density reducing additives may include any microspheresthat are compatible with a subterranean cement composition (i.e., thatare chemically stable at least until the cement sets). An example of asuitable microsphere is commercially available from Halliburton EnergyServices, Inc. as “SPHERELITE.” The low-density cement composition mayinclude the microspheres in an amount sufficient to provide a cementcomposition having a density in a desired range. In an embodiment, themicrospheres may be present in the cement composition in an amount fromabout 10 to about 150 percent by weight of the cement. The microspheresmay be added to the cement composition by any suitable method includingdry blending with the cement before the addition of a fluid such aswater, mixing with the fluid to be added to the cement, or by mixingwith the cement slurry consecutively with or after the addition of thefluid. In another embodiment, the microspheres may be pre-suspended inwater and injected into the cement mix fluid or into the cement slurryas an aqueous slurry.

In some embodiments, additional additives may be added to the cementcomposition for improving or changing the properties thereof. Examplesof such additives include but are not limited to accelerants, setretarders, defoamers, weighting materials, dispersants, vitrified shale,fly ash, formation conditioning agents, and combinations thereof.

The foregoing cement compositions may be used in various cementingoperations wherein the cement is displaced into a workspace and allowedto set. In an embodiment, the cement compositions are used in varioussurface applications to cement a workspace at or above the ground, forexample, a workspace encountered in the construction industry. Inanother embodiment, the cement is used in a subterranean workspace, forexample in cementing underground pipe such as sewer pipe or wellborecasing. In one embodiment, the cement compositions may be employed inprimary cementing a wellbore for the recovery of natural resources suchas water or hydrocarbons. Primary cementing first involves drilling awellbore to a desired depth such that the wellbore penetrates asubterranean formation while circulating a drilling fluid through thewellbore. Subsequent to drilling the wellbore, at least one conduit suchas a casing may be placed in the wellbore while leaving a space known asthe annulus between the wall of the conduit and the wall of thewellbore. The drilling fluid may then be displaced down through theconduit and up through the annulus one or more times, for example,twice, to clean out the hole. The cement composition may then beconveyed downhole and up through the annulus, thereby displacing thedrilling fluid from the wellbore. The cement composition sets into ahard mass, which forms a cement column that isolates an adjacent portionof the subterranean formation and provides support to the adjacentconduit.

In another embodiment, the cement composition may be employed in asecondary cementing operation such as squeeze cementing, which isperformed after the primary cementing operation. In squeeze cementing,the cement composition is forced under pressure into permeable zonesthrough which fluid can undesirably migrate in the wellbore. Examples ofsuch permeable zones include fissures, cracks, fractures, streaks, flowchannels, voids, high permeability streaks, annular voids, orcombinations thereof. The permeable zones may be present in the cementcolumn residing in the annulus, a wall of the conduit in the wellbore, amicroannulus between the cement column and the subterranean formation,and/or a microannulus between the cement column and the conduit. Thecement composition sets within the permeable zones, thereby forming ahard mass to plug those zones and prevent fluid from leakingtherethrough.

It is to be understood that the cement compositions can be made bycombining all of the components in any order and mixing the componentsin any sufficient manner known to one of ordinary skill in the art.

To further illustrate various illustrative embodiments of the presentinvention, the following examples are provided.

EXAMPLE 1

A sample of a fluid loss control additive complex was prepared by adding33 grams of ERKOL 40/140 S polyvinyl alcohol and 33 g of sorbitol to 115grams of 2-propanol. 14 grams of water were then added, and theresulting solution was stirred at 170° F. for 2 hours in a flaskequipped with a reflux condenser. A 14.5 gram solution of saturatedboric acid (containing 0.91 g of boric acid) was added. Subsequently,the pH of the solution was adjusted by slowly adding 7.3 grams of a 12.5M NaOH solution. The mixture was allowed to react one hour and then the2-propanol was removed by distillation. The residual water was removedin a vacuum oven. An emulsified fluid loss control additive was preparedby adding 4 grams of PEG 20 sorbitan trioleate and 16 grams of waterinto 42 grams of soy bean oil. 41 grams of the fluid loss controladditive complex were then slowly added into the emulsion. The emulsionwas vigorously mixed for 5 minutes with a mixer. The resulting emulsionwas easily re-dispersable and stable for 48 hours minimum.

EXAMPLE 2

Three cement compositions (Samples 1–3) were prepared. Sample 1 wasprepared by blending 100% Lafarge Class H cement, 42% water, and 0.7%polyvinyl alcohol, with all percentages being by weight of the cement.

Sample 2 was prepared by blending 100% Lafarge Class H cement, 42%water, and 0.7% sorbitol, with all percentages being by weight of thecement.

The emulsified fluid loss control additive of Example 1 was used as afluid loss control additive for Sample 3. Sample 3 was prepared byblending 100% Lafarge Class H cement, 42% water, and 3.5% of theemulsified fluid loss control additive, with all percentages being byweight of the cement.

The Samples were blended according to the procedures set forth in theAPI Recommended Practice for Testing Well Cements 10B, 23^(rd) edition,April 2002 (API 10B).

The thickening time for each Sample was determined with the resultsnoted in Table I. Thickening time tests were performed according to theprocedures in API 10B. Data from the standard API schedule was used toprepare a test schedule to simulate the anticipated well conditions. Thethickening times were obtained at each sample 1–3 using an atmosphericconsistometer of Chandler Engineering Company of Tulsa, Okla. at 170° F.

A fluid loss test was performed on each Sample at 170° F. in accordancewith API 10B, with the results noted in Table I.

TABLE I Cement Composition Samples Thickening Time Fluid Loss at 170° F.Sample 1 2.33 hours 16 ml Sample 2 >7.5 hours None Sample 3 2.58 hours24 ml

It is shown that polyvinyl alcohol alone as the fluid loss controladditive did not affect the thickening time and that sorbitol alone asthe fluid loss control additive retarded the cement composition toprovide a thickening time of more than 7.5 hours, which did not controlfluid loss. The thickening time of 2.58 hours shows that the polyvinylalcohol and sorbitol were crosslinked, with the sorbitol unable toretard the cement composition.

EXAMPLE 3

Cement compositions (Samples 4–6) were prepared using the emulsifiedfluid loss control additive of Example 1. Sample 4 was prepared byblending 100% Class H cement, 42% water, and 0.70% of the fluid losscontrol additive of Example 1. Sample 5 was prepared by blending 100%Class H cement, 42% water, and 1.0% of the fluid loss control additiveof Example 1. Sample 6 was prepared by blending 100% Class H cement, 42%water, and 0.17% of the fluid loss control additive of Example 1. Allpercentages of Samples 4–6 are by weight of the cement. Each of thecement compositions were prepared under conditions set forth in API 10B.

An API 10B fluid loss test was performed on Samples 4–6 with the resultsindicated in Table II.

TABLE II % Dosage of Emulsion by Weight Fluid Sample Number of CementRheology Readings Loss Sample 4 1.5% 155-83-57-31-6-4 10 ml Sample 51.0% 185-102-71-41-20-8 20 ml Sample 6 0.7% 200-129-100-69-25-19 56 ml

As developers of fluid loss control additives typically target an API10B fluid loss of below about 100 ml, it can be seen that cementcompositions having fluid loss control additives with cross linkedpolyvinyl alcohol and sorbitol provide a desirable level of fluid losscontrol.

While preferred embodiments of the invention have been shown anddescribed, modifications thereof can be made by one skilled in the artwithout departing from the spirit and teachings of the invention. Theembodiments described herein are exemplary only, and are not intended tobe limiting. Many variations and modifications of the inventiondisclosed herein are possible and are within the scope of the invention.Use of the term “optionally” with respect to any element of a claim isintended to mean that the subject element is required, or alternatively,is not required. Both alternatives are intended to be within the scopeof the claim. Use of broader terms such as comprises, includes, having,etc. should be understood to provide support for narrower terms such asconsisting of, consisting essentially of, comprised substantially of,etc.

Accordingly, the scope of protection is not limited by the descriptionset out above but is only limited by the claims which follow, that scopeincluding all equivalents of the subject matter of the claims. Each andevery claim is incorporated into the specification as an embodiment ofthe present invention. Thus, the claims are a further description andare an addition to the preferred embodiments of the present invention.The discussion of a reference in the Description of Related Art is notan admission that it is prior art to the present invention, especiallyany reference that may have a publication date after the priority dateof this application. The disclosures of all patents, patentapplications, and publications cited herein are hereby incorporated byreference, to the extent that they provide exemplary, procedural orother details supplementary to those set forth herein.

1. A method of cementing a wellbore in a subterranean formation,comprising: displacing a cement composition into the wellbore, whereinthe cement composition comprises cement, water, and a fluid loss controladditive comprising a polymer and a sugar connected by a pH-sensitivecrosslink; and allowing the cement composition to set.
 2. The method ofclaim 1, wherein the fluid loss control additive is present in thecement composition in an amount from about 0.01 to about 10.0 percent byweight of the cement.
 3. The method of claim 1, wherein the fluid losscontrol additive comprises a weight ratio of polymer to sugar of fromabout 1:3 to about 10:1.
 4. The method of claim 1, wherein thepH-sensitive crosslink is achieved through a polyvalent cation.
 5. Themethod of claim 4, wherein the polyvalent cation comprises a Group IIIAelement or a Group IVB element.
 6. The method of claim 4, wherein thepolyvalent cation comprises boron.
 7. The method of claim 4, wherein thepH-sensitive crosslink is achieved through the polyvalent cation in anamount from about 0.001 to about 5 percent by weight of the polymer. 8.The method of claim 1, wherein the sugar comprises a sugar alcohol. 9.The method of claim 8, wherein the sugar alcohol comprises sorbitol,maltitol, isomalt, xylitol, lactitol, hydrogenated starch hydrolysate,or combinations thereof.
 10. The method of claim 8, wherein the sugaralcohol comprises sorbitol.
 11. The method of claim 1, wherein thepolymer comprises a polyalcohol, an alpha hydroxy acid, a 1,2 amine, orcombinations thereof.
 12. The method of claim 1, wherein the polymercomprises polyvinyl alcohol.
 13. The method of claim 1, wherein thefluid loss control additive further comprises an emulsion, wherein theemulsion comprises a carrier fluid and the crosslinked polymer andsugar.
 14. The method of claim 13, wherein the carrier fluid is ahydrophobic carrier fluid.
 15. The method of claim 13, wherein thecement composition contains the emulsion in an amount from about 0.02 toabout 3 percent by weight of the cement.
 16. A method for reducing fluidloss from a cement composition, comprising: providing a cement and afluid loss control additive, wherein the fluid loss control additivecomprises a polymer and a sugar connected by a pH-sensitive crosslink;mixing the cement, fluid loss control additive, and water to form thecement composition; and placing the cement composition in a wellbore ina subterranean formation.
 17. The method of claim 16, wherein the fluidloss control additive is present in the cement composition in an amountfrom about 0.01 to about 10.0 percent by weight of the cement.
 18. Themethod of claim 16, wherein the cement composition comprises a weightratio of polymer to sugar of from about 1:3 to about 10:1.